Phosphoramidate esters of dibromoneopentylglycol

ABSTRACT

Novel phosphoramidate esters of dibromoneopentylglycol are prepared, e.g. by reacting a benzene solution of 2,2&#39;&#39;-bis bromomethyl-1,3-propanediol with POCl3 to make an intermediate. Dimethylamine is reacted with the intermediate to made the following structure: These materials are useful as flame retardants when blended into polymeric materials.

nite States Patent 91 [111 3,887,655

Shim June 3, 1975 PHOSPHORAMIDATE ESTERS 0F 3,597,503 8/1971 Wilson et a1. 260/937 DIBROMONEOPENTYLGLYCOL Inventor: Kyung S. Shim, irvington, N.Y.

Stauffer Chemical Company, Westport, Conn.

Filed: Aug. 20, 1973 Appl. No.: 389,829

Related U.S. Application Data Continuation of Ser. No. 252,680, May 12, 1972, abandoned, which is a continuation of Ser. No. 35,269, May 6, 1970, abandoned.

Assignee:

U.S. Cl. 260/937; 106/138; 260/45.8 N; 260/45.9 R; 260/239 D; 260/239 EP;

Int. Cl. C07f 9/24 Field of Search 260/937 References Cited UNITED STATES PATENTS 5/1962 Wadsworth et a1 260/937 5/1962 Wadsworth et a1...... 260/937 12/1964 Bartlett 260/937 OTHER PUBLICATIONS Edmundson et al., Index Chemicus, Vol. 32, No. 12, (3-17-69), 109119.

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Richard L. Raymond [5 7] ABSTRACT These materials are useful as flame retardants when blended into polymeric materials.

3 Claims, No Drawings 1 PI-IOSPHORAMIDATE ESTERS OF DIBROMONEOPENTYLGLYCOL CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a continuation of Ser. No. 252,680, filed May 12, 1972, now abandoned, which in turn was a continuation of the parent application, Ser. No. 35,269, filed May 6, 1970, now abandoned.

This invention relates to novel compositions of matter. In particular, this invention relates to the preparation of esters of dibromoneopentylglycol. The novel phosphoramidate esters of dibromoneopentylglycol prepared in accordance with the present invention are useful particularly as flame retardants. The novel halophosphonate esters of dibromoneopentylglycol are intermediates in the preparation of compositions including the phosphoramidate esters of this invention.

The novel phosphoramidate esters of dibromoneopentylglycol are represented by the following formula:

In the above formula, X is oxygen or sulfur; R and R are the same or different alkyl group having from 1 to 8 carbon atoms and preferably from 1 to 4 carbon atoms, hydrogen, or phenyl. R and R can form a single alkylene ring compound containing 2, 4, 5 or 6 carbon atoms such as the aziridine, piperidine, pyrolidine, or hexamethyleneimine rings.

The novel compounds of the present invention are efficient flame retardants when incorporated in various polymers or other flammable substrates. In general, the novel compositions of this invention are useful as flame retardants in a wide range of compositions such as, for example, polymethylmethacrylates, cellulose acetates, rayon, polyesters, polyphenyleneoxides, flexible as well as rigid polyurethanes, polystyrene, ABS-type polyllr (1H,-

Br (3H,;

mers, polyethylene, polypropylene, nylon, polyvinyl chloride, polyethylene oxide, polypropylene oxide, paper, textiles such as cotton fabrics and the like.

Dr CH;-

Br CH,"

CH; CH

The amount of novel compound which is necessary to give commercially satisfactory flame retardance in any particular polymer or substrate system will vary over a wide range. Usually between about 1 to 50% (on a weight basis) of the flame retardant material is employed. Preferably, between about 5 and about 10% is used. In general, any suitable known method of incorporating flame retardant materials may be employed. Blending the additive materials with the prepolymers prior to formation of the polymeric material is one preferred method of achieving the desired, final flame retarded polymer.

While it is generally recognized that compositions containing bromine improve the flame retardants of polymers many bromine containing compounds are unsatisfactory by reason of their instability. These compounds are known to dehydrobrominates when incorporated in polymers and permitted to stand at room temperature. The compositions of the present invention exhibit improved stability, particularly improved light stability, as well as excellent fire retardancy characteristics.

The present invention also provides novel intermediates for the preparation of compounds including the phosphoramidate esters. The novel intermediates have the following formula:

Br CH CH In the above formula, X is oxygen or sulfur and Y represents chlorine or bromine. In addition to being useful phorus oxy halide in a suitable solvent at a temperature, for example, between room temperature and C. until hydrogen halide evolution is essentially complete in order to make the halophosphonate ester of dibromoneopentylglycol.

The general method of preparation of the novel compounds of this invention is represented by the following equations:

incu, (2H2 0 R CH O X wherein X, Y, R and R have the significance previously stated. Suitable amines include n-butylamine, methylamine, ethylamine, propylamine, cyclohexylamine, aniline, di-n-butylamine, di-i-propylamine, dimethylamine and diethylamine.

Having described the invention in general terms, reference is now made to specific examples which should not be construed as unduly limiting thereof:

EXAMPLE 1 B1. CH3 CH2 O \u C l Cl B1. CH CH O A benzene solution (450 ml. of benzene) of 2,2'-bisbromoethyl-l,3-propanediol (261.8 grzl mol) is reacted with POCl (153.3 gr:l mol) at 50C. over a period of 6 hours until HCl gas ceased to evolve. NMR and IR analysis confirms the structure set forth above.

Phosphorus Analysis calculatedzwt. P 9.05

found: wt. P 9.00

EXAMPLE 2 Br ca;- ca o ii c l c1 mca, ta o This compound is made by the same procedure as set forth in Example 1 except that PSCl is used instead of POCI EXAMPLE 3 Bi. CH; CH

C Br CH/ CH- Br O This compound is made by the same procedure as set out in Example 1 except that POBr is used instead of POCl EXAMPLE 4 Br cu CH o 0 /cas /c\ /1* Br ca on o ca Analysis: Found Theory MW 351 By 350.8

Mass 5 Spec.

%Br 45.0 45.5 %P 9.0 6.82 %N 4.2 3.99

10 EXAMPLE 5 The following compounds are prepared by the procedures of Examples 1 and 4 by substituting the appropriate phosphorus trichloride and amine reactants: l5

Br CH; (2H; o C H \;g F\ incu,-. cm.- 0

Hr cm cu- 0 can- /P N Br CH3 CH,- 0 C ll Br CH; ra, 0 0 ca.

\u c ,1 N

Bl CH; CH; 0 03H! Hr cu, CH 0 c n a C\ /P N Br CH ca 0' c n,

Br CH CH, o 0 H O k Cv P N Br CH3 CH2 O (10) BL CH? /CH; CHp

/c\ /1 n BI. CH3 CH3 O CH;

Br CH? CH;; O O CH:

l u \CHZ! /c\ 1 N cn Br CH CH 0 Cli CH;

Br on, 011.1

The compounds produced by Example 4 was evaluated by incorporating or adding the specified amounts thereof to the materials shown in the following tables. The tire retardancy of the resulting materials was then quantitatively evaluated by determining their Limiting Oxygen Index (LOI) by means of the procedure described by Fenimore and Martin in the November 1966 issue of Modern Plastics. In brief, this procedure directly relates flame retardancy to a measurement of the minimum percentage concentration of oxygen in a oxygenmitrogen mixture which permits the sample to burn; the LOI being calculated as follows:

Thus, a higher L0! is indicative of a higher degree of flame retardancy.

TABLE 1 LOl in Rayon wt. Add on LOl i Br CH3 l8.2 29.54 PN 17.2 28.28 5, 0 CH 7.9 25.46

T 19.7 27.70 (Cl-l CH-Cl-l O) P l5.8 25.90 8.8 24.50 BR Br 3 7)2]n 18.8 26.4 8 22.5

TABLE 2 Flame test in flexible polyurethane foam wt.% Add On Flammability 3 Q i Br 0 CH :PN: 10 Self extinguishing 0 CH (ClCl-l Cl-l O) P O Burn TABLE 3 LOI in 0] hen lene oxide p yp y wt. Add On LOI g Br O CH X 5 29.4 Br 0 CH TABLE 4 L0] in PMMA wt.% Add On LO] 0 Br X03; ,CH;,

20 24.5 Br 0 \CH3 (CHZCHCHZO)3P O l l 20 23.3 Br Br TABLE 5 Flame test in polyethylene terephthalate (polyester) wt.% Add On Flammability tion in a polymeric material. Methyl methacrylate by weight) was mixed with (20% weight) N,N'-dimethylphosphoramidate ester of dibromoneopentylglycol and 200 ppm of azo-bis isobutylonitrile at room temperature. The resulting mixture was heated at 80C. in a closed vessel over a period of 6 hours to obtain a flame retarded polymethylmethacrylate. The L0! results are given in Table 4, supra.

What is claimed is:

1 Compositions of matter in accordance with the formula:

Br CH CH, 0 R

\/ c P n Br on, ca, 0 RP wherein X is oxygen or sulfur, R and R are the same or different and are selected from the group consisting of alkyl containing from 1 to 10 carbon atoms; hydrogen, and phenyl.

2. The composition of claim 1 wherein X is oxygen, and R and R are each methyl.

3. The composition of claim 1 wherein X is sulfur, and R and R are each ethyl.

E r I t ,4

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 5,887,655

DATED June 5, 1975 |N\/ENTOR(S) Kyung S, Shim It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Page 1, change "irvington' to Irvington Page 1, Abstract, line 5, Change "made" to make Column 2, line 57, after "flame" delete 'retardant of" and after "retardants" insert of the Column 3, line 17, change "loromoethyl-l,5--pro1panediol to bromomethyll,5-propanediol Signed and Scaled this second I) ay Of September 1975 [SEAL] Arrest.-

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner uj'Patenrs and Trademarks 

1. COMPOSITIONS OF MATTER IN ACCORDANCE WITH THE FORMULA:
 1. Compositions of matter in accordance with the formula:
 2. The composition of claim 1 wherein X is oxygen, and R1 and R2 are each methyl. 